Syntheses, X-ray Structural Characterizations, and Thermal Stabilities of Two Nonclassical Trinuclear Vanadium(IV) Complexes, (V3(μ3-O)O2)(μ2-O2P(CH2C6H5)2)6(H2O) and (V3(μ3-O)O2)(μ2-O2P(CH2C6H5)2)6(py), and Polymeric Complexes of Stoichiometry (VO(O2PR2)<su

Maass, John S.; Chen, Zhichao; Zeller, Mat­thias; Tuna, Floriana; Winpenny, Richard E. P.; Luck, Rudy L.

doi:10.1021/ic201259u

Cited by 12 publications

(1 citation statement)

References 43 publications

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“…The preformed oxo-centered transition metal based triangular complexes are used as a precursor to reveal fascinating coordination complexes with excellent electronic and magnetic properties. For example, several oligonuclear iron, manganese, chromium, and ruthenium complexes ranging from 3 to 84 metal centers containing complexes were isolated using their respective oxo-centered triangular homovalent or mixed valent metal precursor . Among the numerous metal clusters isolated, common bridging ligands such as oxo, hydroxo, methoxo, phenoxo, carboxylates, etc.…”

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confidence: 99%

Unusual Methylenediolate Bridged Hexanuclear Ruthenium(III) Complexes: Syntheses and Their Application

et al. 2018

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Three structurally analogous hexanuclear ruthenium(III) complexes were isolated with the general molecular formula of [Ru6 III(O)2(μ4-η2-η2-CH2O2)(t-BuCO2)12(L)2] where L = pyridine (1) or 4-dimethylamino pyridine (DMAP; 2) or 4-cyanopyridine (3). Complexes 1 and 3 were solved in the tetragonal I4̅c2 and P4 1212 space group, respectively, while 2 crystallized in the monoclinic system with P2 1 /c space group. In all three complexes, two oxo-centered Ru(III) triangles were bridged by a unique and a rare methylenediolate (CH2O2)2–) ligand. This (CH2O2)2– group is reported to be an intermediate, which is not isolated in its metal-free form, to date, as it is unstable. Control experiments performed evidently reveal that the unique reaction condition followed is mandatory to isolate 1–3 and the origin of (CH2O2)2– is unknown at the moment, as no precursor was used to form this intermediate. The presence of (CH2O2)2– identified through X-ray diffraction was further unambiguously confirmed by various 1D (1H and 13C) and 2D-NMR (HSQC, TOCSY, NOESY, and DEPT) spectroscopies. Direct current (dc) magnetic susceptibility measurements performed on 1 and 2 reveal the predominant antiferromagnetic exchange interaction between the Ru(III) centers result in a diamagnetic ground state at 2.0 K. The paramagnetic influence of 1–3 at room temperature evidently felt by the 1H nuclei of the (CH2O2)2– unit predominates compared to other NMR active nuclei in the complexes. The presence of an electron donating or withdrawing substituent on the terminal pyridine results in significant change in the dihedral angle of two oxo-centered triangular (Ru3O−) planes. The change in the structural parameters of 1–3 due to the substituents markedly reflected on the absorption profile and redox behavior, which are systematically investigated. Preliminary galvanostatic charge/discharge cycling experiments performed on a representative complex (3) suggest that 3 can be a promising candidate to employ as an effective multiple electron charge carrier in a nonaqueous redox flow battery.

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Section: Introductionmentioning

confidence: 99%

Unusual Methylenediolate Bridged Hexanuclear Ruthenium(III) Complexes: Syntheses and Their Application

et al. 2018

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Systematic Synthesis of Di‐, Tri‐, and Tetranuclear Homo‐ and Heterometal Complexes Using a Mononuclear Copper Synthon with a Tetradentate Amino Alcohol Ligand

et al. 2016

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The reaction of Cu(NO3)2·3H2O with an N2O2 tetradentate amino alcohol, N,N‐dibenzyl‐N′,N′‐bis(2‐hydroxyethyl)ethylenediamine (H2L), afforded the mononuclear copper complex [Cu(H2L)(NO3)](NO3) (1), which has been used to construct a series of di‐, tri‐, and tetranuclear homo‐ and heterometallic complexes. Complex 1 dimerized in the presence of NEt3 to form the Cu2 complex [Cu2(HL)2](NO3)2 (2) by the deprotonation of one of the two hydroxy groups in the H2L ligand. The reaction of 1 with Cu(OCOH)2 in the presence of NEt3 afforded the Cu3 complex [Cu3(HL)2(OCOH)2](NO3)2 (5). The metalloligand {Cu(HL)}+ derived from 1 reacted with M(OAc)2 (M = Cu, Co, Zn, Ni) in the absence of NEt3 to form the asymmetric CuM dinuclear complexes [CuM(HL)(OAc)(NO3)2] [M = Cu (3a), Co (3b), Zn (3c), Ni (3d)], whereas in the presence of NEt3 a unit of M(OAc) was captured by two metalloligands to give the bent CuMCu trinuclear complexes [Cu2M(HL)2(OAc)2(NO3)](NO3) [M = Cu (4a), Co (4b), Mn (4c)], which were further transformed into the linear CuMCu trinuclear complexes [Cu3(HL)2{(PhO)2PO2}2](NO3)2 (7a) and [Cu2M(HL)2{(PhO)2PO2}2(MeOH)2](NO3)2 [M = Co (7b), Mn (7c)] with the aid of diphenyl phosphate bridging ligands. When (PhO)PO2(OH) was used as an auxiliary bridging ligand in the reaction of 1 with M(OAc)2 and NEt3, the Cu2M2 tetranuclear complexes [Cu2M2(HL)2{(PhO)PO3}2(NO3)2] [M = Co (8a), Zn (8b)] were synthesized. These results demonstrate that the mononuclear copper synthon with the N2O2 tetradentate amino alcohol ligand {Cu(H2L)}2+ generates the quite useful metalloligand {Cu(HL)}+ by the deprotonation of a hydroxy group, and subsequent reactions lead to the construction of a series of homo‐ and heterometal complexes containing Cu2, CuM (M = Cu, Co, Zn, Ni), bent‐CuMCu (M = Cu, Co, Mn), linear‐CuMCu (M = Cu, Co, Mn), and Cu2M2 (M = Co, Mn) cores in a systematic and selective manner.

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Methoxido‐Bridged Lacunary Heterocubane Oxidovanadium(IV) Cluster with Azo Ligands: Synthesis, X‐ray Structure, Magnetic Properties, and Antiproliferative Activity

et al. 2022

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The new μ 3 -methoxido bridged trinuclear vanadium(IV) complexes [V IV 3 O 3 (μ 3 -OMe)(μ 2 -OMe) 3 (L 1,2 ) 2 ] (1 and 2) have been synthesized using the azo ligands 1-(2-(thiazol-2yl)diazenyl)naphthalene-2-ol (HL 1 ) and 2-(2-(thiazol-2yl)diazenyl)-4-methylphenol (HL 2 ). X-ray crystallography revealed a trinuclear structure with a lacunary heterocubane {(VO) 3 (μ 3 -OMe)(μ 2 -OMe) 3 } 2 + core unit for complex 1, which contains a central μ 3 -methoxido bridge. All three vanadium centers are in a slightly distorted octahedral coordination environment. Magnetic and theoretical studies reveal an antiferromagnetic coupling between the three vanadium(IV) centers within the triangular arrangement in 1. The complexes were also screened for in vitro cytotoxicity study against HeLa and HT-29 cancer cell lines. The results indicated that both the complexes are cytotoxic but possess varying specificity towards different cell types.

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Cited by 12 publications

References 43 publications

Unusual Methylenediolate Bridged Hexanuclear Ruthenium(III) Complexes: Syntheses and Their Application

Unusual Methylenediolate Bridged Hexanuclear Ruthenium(III) Complexes: Syntheses and Their Application

Systematic Synthesis of Di‐, Tri‐, and Tetranuclear Homo‐ and Heterometal Complexes Using a Mononuclear Copper Synthon with a Tetradentate Amino Alcohol Ligand

Methoxido‐Bridged Lacunary Heterocubane Oxidovanadium(IV) Cluster with Azo Ligands: Synthesis, X‐ray Structure, Magnetic Properties, and Antiproliferative Activity

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